JPS60157106A - Capacitor with dielectric having multifunction acrylate polymer, method of producing and chemical substance for dielectric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to electrical capacitors. More particularly, the present invention relates to a novel capacitor having a multifunctional acrylate polymer dielectric and a method of manufacturing the same.

[Technical background of the invention]

With the development of small electronic components and circuits, the need for small capacitors with large capacitance per unit volume and high temperature resistance has increased. In particular, in order to retain energy within the capacitor during operation, this type of capacitor must have a low dissipation factor over a wide temperature range.

However, a single capacitor that can satisfy various usage conditions and demands has not been known or used. Therefore, over the years, a number of products have been developed along three main manufacturing processes: ceramic, mold, metallized film, and electrolyte.

However, most of these are limited to use above about 100 micropts.

Additionally, each has significant drawbacks. For example, solid electrolyte capacitors and ceramic multilayer capacitors generally have large loss factors and undesirable changes in characteristics.

On the other hand, metallized film capacitors have significant volumetric efficiency limitations and no possibility of surface mounting.

In short, all capacitors currently in use have deficiencies in various aspects, including size, long-term electrical stability, and ability to operate satisfactorily in the temperature range of 230-280°C.

This technological development has therefore been accompanied by a compromise in the general recognition that problems need to be better solved. With technology in this state of development, the aforementioned need continues to persist.

No. 620.647, filed June 14, 1983, discloses a novel capacitor structure with particularly advantageous properties that can meet a wide range of usage conditions and demands. There is.

According to this structure, the conductive layers are arranged in sequence in an offset manner to define a central capacitance region of the deposited dielectric stretched layer, and a dielectric coating is disposed on each of said layers, and each layer of the capacitance region is connected to said dielectric layer. so that they are separated by a body coating at approximately regular intervals.

Also, the laying down of the coating is controlled so that it slopes towards a cut line that is substantially spaced from the two separate parts of the central capacitance region. The layer is
It is laid so that it extends beyond the cutting line, so that each successive layer welds into separate terminal portions at regular intervals of m.

Furthermore, the spacing of the cutting lines is such that the top dielectric coating of the capacitor has a horizontal dimension for laying the final layer from the capacitance area towards the terminal area.

The contents of said application are incorporated herein by reference to the application number.

[Purpose of the invention]

A first object of this invention is to provide a new capacitor having an improved resin dielectric and a method of manufacturing the same.

A second object of the present invention is to provide a capacitor that can be used under a wide range of conditions and has a wide range of applications.

A third object of the invention is to provide a capacitor with a low loss factor, relatively little change in capacitance value over a wide temperature range, and a wide range of operating conditions.

A fourth object of this invention is to provide a novel ester monomer and its polymer.

A fifth object of the invention is to provide ester motes which, upon polymerization, form materials suitable for use as dielectrics.

A sixth object of this invention is to provide an ester monomer whose polymer has a low loss factor over a very wide temperature range.

A seventh object of this invention is to provide a polymeric dielectric material that can be used in thin film capacitors.

An eighth object of the invention is that the film is easy to lay down as a thin film, which film can be subsequently polymerized by irradiation or other methods to form a layer for use as a dielectric in a thin film capacitor. The object of the present invention is to provide such ester monomers.

Other objectives may be in part self-evident or will become apparent from the description below.

[Embodiments of the invention]

To achieve the above object, according to the present invention, a capacitor comprises two electrodes separated by a dielectric member, the dielectric member comprising at least one polyfunctional acrylate polymer having the chemical formula: There is. However, in this case R1 is a hydrocarbon or substituted hydrocarbon radical containing at least 4 carbon atoms, and R2 is hydrogen or 1 to 5
and n has a value between 2 and 6.

The electrodes of the capacitor according to the present invention are made of materials known in the art and are formed in known shapes. Common conductive materials used as electrodes are aluminum, copper, zinc, tin, stainless steel, and their alloys with aluminum.

As described above, the dielectric member is a polyfunctional acrylate polymer having the chemical formula (2). In this chemical formula,
R1 is a hydrocarbon or substituted hydrocarbon radical containing at least 4 carbon atoms. The types of possible substituents will be apparent to those skilled in the art. In addition, in general, this type of substitution moiety includes a strong substitution moiety that has only a slight influence on the electrical properties of the molecule.

For example, such substituents are hydroxy, alkoxy, carbalkoxy, and also nitrile substituents. However, in many cases R is an unsubstituted hydrocarbon radical.

R1 contains at least 4 carbon atoms. In this case there is no upper limit to the number of carbon atoms. It is within the scope of this invention to use complexes of formula I, for example, where R is a polymeric radical containing on the order of 500 carbon atoms, preferably about 300 or more carbon atoms.

The R1 radical may include aliphatic, cycloaliphatic, or aromatic moieties, or mixtures thereof. However, it is desirable that all moieties present therein be aliphatic, cycloaliphatic, or both.

R2 can be hydrogen or an alkyl group containing 1 to 5 carbon atoms, as described above.

Often R is hydrogen or methyl, essentially hydrogen.

As such, the term "acrylate" as used herein includes both acrylates and alpha-substituted acrylates, including methacrylates and the like. however,
Acrylates (eg, complexes where R2 is hydrogen) are commonly used. The value of n is between 2 and 6, often 2 or 3.

As is clear from the above, the complex of chemical formula (2) generally contains acrylic acid, methacrylic acid, etc., such as acid chlorides, anhydrides, lower alkyl esters, or functional derivatives thereof.
It is formed by esterification with various complexes containing R. For example, such composites are polyhydroxy composites and polyepoxides. Particularly useful polyfunctional acrylates of formula (2) are as follows.

(1) about 4 to 20 carbon atoms, exemplified by neopentyl glycol, trimethicolpropane, 1,6-hexanediol, and α,W-diol mixtures having 12 to 20 carbon atoms in one average chain length. Acrylates of aliphatic polyhydroxy complexes containing carbon atoms (2) Acrylates of polymers having groups capable of reacting with acrylic acid or its derivatives. Illustrative are dienes with hydroxy end groups such as polybutadiene having a number average molecular weight of about 1000-5000.
It is a polymer.

(3) Acrylates of aromatic dieboxides and polyepoxides exemplified by derivatives of 2',2-bis(4-hydroxy-phenyl)propane or "bisphenol A".

A number of commercially available polyfunctional acrylates can be used to form the dielectric of the capacitors of this invention. These are listed below, many of which are identified by trademarks.

(1) Trimethicolpropane triacrylate (2)
Neohentyl glycol diacrylate (3) Bisphenol A diacrylate (4) Celanese "Cellrad 3700 J (0elra)"
d 3700”), a diacrylate of a diepoxide derived from a bisphenol.

(5) [Sartome S R-349J
r 5Rr-349), ethoxylated bisphenol A0(6) Sartoma [Chemlink 2000 j (Sa
diacrylates of α,W-alkanediols having an average number of carbon atoms of 14 to 15.

(7) Arco [Poly b d J (Arco” Po
1y bd ”) butadiene resin having hydroxy end groups with a number average molecular weight of about 3000.

The use of single polyfunctional complexes to form dielectrics
Although within the scope of this invention, copolymers formed by mixing two or more such composites are often used.

This allows the loss factor to be smaller than when only polyfunctional acrylate is used. Moreover, the physical properties of the material can be improved.

For example, the viscosity of the monomer structure can be lowered, making it easier to adhere to it.

It is also within the scope of this invention to use a copolymer formed from a mixture of at least one complex of formula I and at least one monoacrylate of formula (). However, here, R2 is as described above,
R3 is also a hydrocarbon or substituted hydrocarbon radical, usually containing 4 to 25 carbon atoms.

Monoacrylates of formula (1) are various acrylic derivatives of fatty acids containing substituents such as cyclohexyl methacrylate and carbomethoxy or nitrile. A typical copolymer of the conjugate of formulas I and 1 will have a conjugate of formula H in equilibrium with the conjugate of formula
50% by weight, often about 15-35% by weight.

With such commercially available acrylates, it is often a good idea to remove residual acrylic acid, other ionic compounds, and impurities that may be present when received from the vendor.

Such impurities are immediately removed, such as by using absorption columns or ion exchange resins.

Examples of multifunctional acrylate structures forming polymers suitable as dielectrics for use in the capacitors of this invention are shown in the following table.
and shown in Table ■. All numbers in these tables are volume percentages.

Table ■ Contents Example 123 ゛1Polybd'' diacrylate 10 (150-°°Chemlink 2000'' 5o11ooI) Elm N 1
According to an example of the capacitor of this invention, the dielectric material is
A polymer of at least one polyfunctional acrylate of Formula I. Here, RiJ.

hydrogen or methyl, and n has a value between 2 and 4. R is also an aliphatic radical, an alicyclic radical, or an alicyclic mixed radical having about 10 to 40 carbon atoms and optionally containing about three or more nonconjugated olefinic bonds.

The R 2 radical in this example is an aliphatic radical, an alicyclic radical, or an alicyclic mixed radical. Also,
The radical optionally contains about three or more non-conjugated olefinic bonds and contains about 10 to 40 carbon atoms.

Polyhydroxy compounds are straight chain compounds such as hexadecanediol and octadecanediol,
It has a hydroxy group placed somewhere along the chain and its branched chain isomers. Here, "branched chain" means that at least one carbon atom is present in a branch.

Thus forms like HO(Of(,) OH and 5 OH are unbranched and dusty, while OHs (OH2)a OH(OH2)60H20H and CH,0H OH30H.

is branching.

An exemplary first population of polyhydroxy compounds in this example is branched by containing at least 18 carbon atoms in a single chain, i.e. at least 18 carbon atoms. It is characterized by being continuously connected without branching. In particular, suitable polyfunctional acrylates obtained from these have the following chemical formulas O 12 and (■) 1 E 16°, where shi and S are each 7 or 8, and the sum of r and s is 15. These can be obtained, for example, by acrylic acid esterification of hydroformylation products of oleic acid as described in US Pat. No. 4,243,818.

Other suitable compounds include the 1,12-
Octadecanediol diacrylate.

A first group of suitable polyhydroxy compounds also includes novel mono-compounds and mixtures. In particular, phosphorus contains about 20 to 40 carbon atoms, and in some cases about 3
A mixture of at least one aliphatic or alicyclic radical containing three or more non-conjugated olefinic bonds.

At least 40%, and preferably at least 50, of the total number of R1 radicals are cycloaliphatic. Therefore, polyhydroxy compounds can be fully cycloaliphatic,
Or it can be a mixture of aliphatic and alicyclic compounds satisfying these percentage limits.

To form such polyhydroxy compounds, it is often convenient to reduce at least one corresponding polycarboxylic acid or ester thereof which is saturable or which may contain olefinic linkages.

Typical polycarboxylic acids suitable for the purposes of this invention are linoleic acid dimers (hereinafter referred to as "dimer acids"), or base acids that typically contain 92 or more olefinic linkages per molecule. Typically, it is a mixture of acrylic acid, monocyclic and dicarboxylic acids.

A particularly suitable dimer acid is “Empol 101 QJ
EmeryIn (Empol 1010) trademark
sold by industries.

Kirk Os? Encyclopedia of C by Kirk Othrner
Chemical Technology) 3rd edition, 7th edition
According to Vol. 768-770, the structure of a typical molecular species present in the methyl ester of a dimer acid is as follows.

(V) CH3(OH2)70H(OH2)s 0OO
CH3CH3(CH2)7C=CH(OH2)7. C0
0CH3 Thus, the free dimer acid clearly comprises the free dicarboxylic acid with the corresponding structure.

Esters of Formulas V, ■, ■, cholera corresponding free acids, and similar polycarboxylic acids and esters can be reduced by well-known methods. For example, it can be reduced with hydrogen in the presence of a hydrogenation catalyst and with lithium aluminum hydride to form dimers used to prepare multifunctional acrylates.

Depending on these acids or esters, or similar acids or esters, the reduction product can be saturated or contain olefinic linkages. For example, reduction with lithium aluminum hydride usually does not affect olefinic bonds, but some hydrogenation methods (eg, under palladium catalysis) reduce them to saturated bonds.

In this way, dimers of the following chemical formulas can be produced by reduction of the compounds of the chemical formulas V, V+, and (2), respectively.

(■) CH3(CH2)7CH(CH2)8CH20H0H3
(OH2)7Ci2':mCH(OH2)7C! H2
0H(H) (H) (■) (H) (44:) However, here, the dotted line and the hydrogen atoms in the brackets indicate that the corresponding carbon-carbon bond is a single bond or a double bond depending on the reduction method. This indicates that it may occur.

It has often been found that compounds containing only single bonds have properties that are somehow more advantageous than those of similar double bond compounds. A diol mixture of this type suitable for the purpose of this invention is available under the trade name "Dimerol J".
It is sold by Henkel C1orporation.

Other suitable polyhydroxy compounds of this first group of examples can be formed by various acrylic acid-unsaturated fatty acid condensation product reductions.

These polyhydroxy compounds can be exemplified by the following chemical formula (). However, here, m is a value between 3 and 5, for example, p is a value between 7 and 9, and the sum of m and p is 12.

A commercially available dicarboxylic acid that can be reduced to a diol with the chemical formula lxl is available under the trade name "Westvaco 155° Diazide J (
We++tvaco 1550 Diacid) is an adduct of linoleic acid and acrylic acid with the chemical formula.

This is also described on page 779 of Kirk Kosma, supra.

An exemplary second group of polyhydroxy compounds consists of R consisting of 1,2-alkanediols having the formula: However, here, R4? 'i' is an alkyl group containing about 8 to 28 carbon atoms.

R fucical suitable for the purpose of this invention are, for example, 1-octyl, 2-methylheptyl, 1-nonyl, 2,3-dimethylhebutyl, 1-7"yl, 2-dodecyl, 1-tetradecyl, 1-octadecyl. , 1-eicosyl, and 1-tocosyl.

Mata is suitable as a radical R4 having the chemical formula R50H2. Here, 几5 is an alkyl group, especially about 7 to 2
7 and often straight chain alkyl groups having about 9 to 17 carbon atoms.

Also, one embodiment of the capacitor of the present invention is such that the dielectric is a polymer of Formula I and a novel mixture of esters having Formula I: where R6 contains about 1 to 20 carbon atoms and is an aliphatic hydrocarbon radical liberated from acetylenic unsaturations and polymerizable ethylenic unsaturations. Further, m is smaller than n and has a value between 1 and 3.

Also, at least 50 of the carboxyl moieties of the structure have the chemical formula (). Such polymers have lower loss factors over a wider temperature range than those mentioned above.

As can be seen from formula Here, R
6 contains about 2 to 19 carbon atoms, free from acetylenic unsaturation and polymerizable ethylenic unsaturation.

The R6 group is preferably an alkyl group, especially 1
It is an alkyl group containing up to 7 carbon atoms and often 2 to 4 carbon atoms. Carboxylic acids of this type include, for example, acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, and oleic acid.

As described in the aforementioned U.S. Application No. 620.647,
Capacitors of the present invention are often produced by methods that include evaporative deposition of monomers followed by polymerization to form the dielectric member.

The vapor deposition conditions for the ester mixtures described above are optimal when the carboxylated moieties contribute approximately equally to the volatility of the ester mixture.

Therefore, it is most desirable that 1,5 have a similar size and molecular weight as the corresponding moiety of the acrylic group. Further, it is particularly desirable that R5 is an ethyl group, that is, R5C00H is propionic acid.

for the total number of carboxylated moieties in these ester mixtures, at least about 50 Ti, usually from about 65 to 99 Ti;
Desirably 70-90% has the chemical formula W. Thus, most of the carboxylated moieties are polymerizable.

Methods of esterification of polyhydroxy compounds will be apparent to those skilled in the art. Thus, alcohols and acids can typically be reacted in a suitable solvent and in the presence of small amounts of acidic esterification catalysts. This catalyst consists of sulfuric acid, p-)
luenesulfonic acid, acidic ion exchange resin, or acidic soil. Typically, a stoichiometric balance of acid is used, and the equivalent ratio of acid to diol is a value between about 1.1:1 and 4:1. After esterification, excess acid can be removed by washing with an aqueous alkaline solution.

In order to minimize the amount of ester of formula % in the aforementioned ester mixtures, it is desirable to form such mixtures by reacting the polyhydroxy complex with two acids sequentially. This may be done in any order, but it is preferable to react with acrylic acid first.

The molar ratio of acrylic acid to other acids is at least 1
:1, often about 165-1.99:1, preferably about 1.7-1.9:1.

Also, since there is some uncertainty as to the exact proportions of the various esters in such mixtures, it is appropriate to define said mixtures by the sequential method by which they are formed.

The esterification reaction is usually carried out at 50-200<0>C, in most cases 60-150<0>C.

In this case, p-methoxyphenol, z, 6-y-t-
It may be desirable to intervene with small amounts of polymerization inhibitors such as butylphenol or 2,4,6-tri-tert-butylphenol.

This acid can be modified by polyfunctional derivatives such as the corresponding acyl no\rides, lower alkyl esters or amides.
Substitutions can be made by appropriately changing the reaction conditions.

The formation of the polyfunctional acrylate and ester mixtures used in this invention is illustrated in the following examples. All percentages are by weight unless otherwise specified.

Example 12 The sum of r and S is 15, and a commercially available diol (Henkel Corpora
tion) by weight, 102 parts (O, A 4 mol),
255 parts of p-methoxyphenol and 15 parts of n-hexane
A mixture of 2.38 parts of p-toluenesulfonic acid in 3 parts was stirred and heated to reflux, and 5.44 parts of acrylic acid (0,
76 mol) was added over several hours. Heating was continued until water was removed by azeotropic distillation.

When the water was removed to the theoretical value, the solution contained 206 parts of n.
- diluted with hexane and extracted five times with three portions of aqueous potassium hydroxy solution and twice with aqueous sodium chloride solution.

By vaporizing hexane and filtering through glass fiber, 1
127 parts (theoretical 92 parts) of diacrylate stabilized by the addition of 100 pp of p-methoxyphenol were obtained.

Example 13 Commercially available triol (Henkel Corpor
ation) i o o g (o', a mole)
, p-methoxyphenol 0.3.9, and toluene 5
A mixture of 2 g of p-)luenesulfonic acid in 00WLl was heated to 120<0>C. Also, acrylic acid 1151n/
! (1.64 mol) was added dropwise. Heating was continued until water was removed by azeotropic distillation.

When the water was removed as per theory, the solution was washed with aqueous potassium carbonate solution and dried. Evaporation of the solvent gave the desired triacrylate as a liquid.

Example 14 Following the method of Example 13, 1,12-octadecanediol diacrylate was formed.

Example 15 96 tusks (2, s) in 3000 ml of tetrahydrofuran
400 g (0.71 moles) of Empol 1010
J (Empol 1010) dimer acid was added dropwise with stirring.

The mixture was heated at reflux for about 40 hours. Also,
Water 96m7! , 15% aqueous sodium hydroxide solution 96
ml and 288 ml of water were added sequentially for neutralization. The neutralized mixture was filtered and the solvent was evaporated from the filtrate to obtain the desired diol.

Diol 200g (0.37 mol), acrylic acid 157+
++/(2,24 mol), p-) luenesulfonic acid a
E s and 0.5 ji p- in toluene of 1000-
A solution of methoxyphenol was heated under reflux until water was removed by azeotropic distillation.

When the stoichiometric amount of water (approximately 13.3 ml) was removed,
The solution was cooled, filtered, and washed several times with dilute potassium carbide solution and once with dilute IJum solution.

This was then dried over magnesium sulfide and the solvent was evaporated to obtain the desired diacrylate as a liquid.

EXAMPLE 16 Following the method of Example 15, Wastvaco 1550 Diacid J was reduced to a diol having the formula 2 with lithium aluminum hydride in tetrahydrofuran. In this chemical formula, m is 5, p is 7, and the dotted line indicates a double bond.

This diol (85 g, 0.25 mol) was reacted with acrylic acid (9 om 111.2 g mol) in toluene solution to obtain the desired diacrylate as a liquid.

Example 17 Following a method similar to Example 13, a liquid diacrylate is formed from a commercially available diol. This diol was formed by hydrogenation of the methyl ester of linoleic acid dimer. Moreover, the main components of this diol have chemical formulas (1), (IX), and (X).

In this chemical formula, dotted lines mainly indicate single bonds.

Example 18 ■, 51 g (0.20 mol) of 2-hexanediol, 100 m/! of acrylic acid! (0,20 mol), p-)luenesulfonic acid 1.5 g and p- in 400 g toluene.
A solution of 2 g of methoxyphenol was heated under reflux for about 24 hours so that the water was removed by azeotropic distillation. The solution was allowed to cool, filtered and washed several times with dilute potassium carbide solution and once with dilute sodium chloride solution.

The solution was then dried and evaporated to obtain the desired 1,2-hexadecanediol diacrylate as a liquid.

Example 19 The sum of r and S is 15, 1026 parts (o, 34 mol) of diol having the chemical formula %, 36 parts (0.5 mol) of acrylic acid, 15 p-methoxyphenol
and 2.33 parts of p-toluenesulfonic acid in 200 parts of n-hexane were heated under reflux to remove water by azeotropic distillation.

After reacting for several hours, 20 parts (0.27 mol) of propionic acid were added and refluxing was continued for 24 hours. The solution was cooled, washed several times with aqueous potassium hydroxide solution, and dried. Evaporation of the solvent yielded the desired mixed acrylic-propionide as a total liquid.

Example 20 Triol 1ooyip-methoxyphenol 25 with the formula %, where the sum of r and S is 15
A solution of 2.33 g of p-toluenesulphonic acid in g1 and n-hexay3oom/in was heated under reflux with stirring and further acrylic acid 509 (0.69 mol) was added.

Heating and stirring were continued for several hours until the water was removed by azeotropic distillation. After several hours of reaction, gropionic acid 249 (0.32 mol) was added and refluxing was continued for several hours. The solution was cooled, washed several times with aqueous potassium hydroxide solution, and dried.

Evaporation of the solvent gave the desired mixed acrylate-propionide (127,19, or 85% of theory) as a liquid.

Example 21 51 parts (0.20 mol) of 1,2-hexadecanediol, 30 parts (0.15 mol) of lauric acid, and 400 parts of hydrene
A solution of 1.5 g of p-toluenesulfonic acid in 1 part was heated under reflux for 24 hours until the water was removed by azeotropic distillation.

Next, 216 parts (0.3 moles) of acrylic acid'f! : Add and continue heating until water stops swirling.

The solution was cooled, filtered, and washed several times with dilute potassium chloride solution and once with dilute sodium chloride solution.

This is dried to obtain the desired 1,2-hexadecanediol.
The solvent is evaporated to obtain the ester mixture as a liquid.

Multifunctional acrylate and ester mixtures can be polymerized under free radical conditions alone or in the presence of other monomers. In this specification, "polymer" means
It includes additions, addition homopolymers, and copolymers with one or more other monomers.

Another aspect of this invention relates to novel polyfunctional acrylate and ester mixture polymers.

Polymerization by the free radical method is carried out by contacting a polymerization initiator with a monomer or monomers in the absence or presence of a diluent at a temperature of about θ to 200°C, in bulk, in solution. It can be carried out in medium, in suspension (suspension) or in emulsion.

Initiating agents suitable for the purposes of this invention include benzyl peroxide,
Tertiary butyl hydroperoxide, acetyl peroxide, hydrogen peroxide, azobisiosoptilonitrile
isobuty-ronitrile), persulfate-bisulfite, persulfate-sulfoxylate, formaldehyde sulfoxylate, chloric acid-sulfite, etc.

Polymerization can also be carried out by irradiation techniques such as ultraviolet light, electron beam, or plasma irradiation.

A large number of polymerizable compounds can be used to form copolymers with multifunctional acrylate and ester mixtures. For example:

(1) Unsaturated alcohols and their esters: allyl, methallyl, crotyl, 1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, 1-phenaryl, and butenyl alcohols, and combinations of such alcohols with saturated acids. , with unsaturated acids, with polybasic acids, with unsaturated polybasic acids, or with aromatic acids.

Saturated acids are, for example, acetic acid, propio/acid, butyric acid, valeric acid, caproic acid, and stearic acid.

Unsaturated acids include, for example, acrylic acid, α-substituted acrylic acid (
Alkyl acrylic such as methacrylic, ethyl acrylic,
(including allyl acrylics such as propyl acrylic and phenyl acrylic) crotonic acid, oleic acid, linoleic acid, and lylic/acid.

Polybasic acids are, for example, oxalic acid, malonic acid, succinic acid, glucuric acid, adipic acid, pimelic acid, sheric acid, azerai/acid, and sebacic acid.

Unsaturated polybasic acids are, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, methylenemalonic acid, acetylene dicarboxylic acid, and aconitic acid.

Aromatic acids include, for example, benzoic acid, phenylacetic acid, phthalic acid,
These are terephthalic acid and benzoylphthalic acid.

(2) Unsaturated acids (examples are given above) and their esters with lower saturated alcohols or with saturated lower polyhydric alcohols.

Lower saturated alcohols are, for example, alcohols such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cef-butyl, tyl-butyl, 2-ethylhexyl, and cyclohexyl.

Examples of saturated lower polyhydric alcohols include ethylene glycol, propylene glycol, tetramethylene glycol,
These are neopentyl glycol and trimethyloprono.

(3) Unsaturated lower alcohols, such as butanediol, and their esters with saturated or unsaturated aliphatic, aromatic, monobasic, and polybasic acids. Each side is as above.

(4) Esters of the above unsaturated acids. In particular, esters of acrylic and methacrylic acids with high molecular weight mono- and polyhydroxy materials.

These materials are, for example, decyl alcohol, isotecyl alcohol, oleyl alcohol, steryl alcohol, epoxy resins UL and polyols derived from polybutadiene.

(5) A vinyl cyclic compound containing the following combinations.

-Styrene/, 0-1 m-1 p- of chlorostyrene, bromostyrene, fluorostyrene, methylstyrene, ethylstyrene, and cyanostyrene.

Mono-, tri-, and tetra-chlorostyrene, bromostyrene, fluorostyrene, methylstyrene, ethylstyrene, cyanostyrene.

monovinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene, allylbenzene, and vinylfuran, vinylpridine, vinylbenzofuran,
Heterocycles such as N-vinylfuransol, N-vinylpyrrolidone, and N-pinyroxazolidone.

(6) Methyl vinyl ether, ethyl vinyl ether
Ether, cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethyl
Unsaturated ethers such as methallyl-ether and allyl ethyl ether.

(7) Unsaturated ketones. For example, methyl vinyl ketone and ethyl vinyl ketone.

(8) Unsaturated amide. For example, acrylamide, methacrylamide, N-methylacrylamide, N-phenylacrylamide, N-allylacrylamide, N-methylolacrylamide, N-allylcapcolactam, diacetone acrylamide, hydroxymethol diacetone acrylamide, and diacrylamide- 2゛Methylpropanesulfonic acid.

(9) Unsaturated aliphatic hydrocarbons. For example, ethylene, propylene, butane, phtadiene, isoprene, 2chlorobutadiene, and α-olefins in general.

0Q Unsaturated alkyl halide. For example, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide,
Allyl chloride and allyl bromide.

α and unsaturated acid anhydride. For example, malein, citracog, itacone, cis-4 cyclohexine-1,2
dicarboxyl and bicyclic (2,2,1)-5hebutene-2,3 dicarboxyl anhydrides.

02 Unsaturated acid halide. For example, the chlorides or bromides of cinnamyl acrylyl, methacrylyl, crotonyl, oleyl, and fumaryl.

α→ Unsaturated nitrile. For example, acrylonitrile, methacrylonitrile, as well as other substituted acrylonitriles.

Due to their polyfunctionality, the acrylate and ester mixtures described herein are capable of crosslinking.
) to form a polymer. Therefore, they can be used in the production of heat-resistant polymer films.

For example, the polymers of this invention can be used to form corrosion-resistant coatings and as inclusions in printing inks. It can also be used as an insulating material in some electrical applications.

This polymer is useful as a dielectric component in capacitors and is suitable for producing capacitors with high efficiency and low loss coefficient over a wide temperature range.

With particular reference to the aforementioned ester mixtures, the present invention is not based on any theory of operation, and it is believed that the R group acts as a plasticizing factor and that there is a change in the conductive properties of the polymer, generally around -20°C to -30°C. It is believed that it lowers some phase transition point that appears at temperatures of .

An embodiment of the invention with a view to use as a dielectric component for capacitors comprises a polymer in which all structural units are derived from the polyfunctional acrylate or ester mixtures of the invention.

Also contemplated are copolymers of the polyfunctional acrylates or ester mixtures with other monoacrylates and polyacrylates. Monoacrylates suitable for the purposes of this invention include, for example, acrylates of higher monohydroxy alcohols such as indecyl alcohol or higher monoepoxides. Here, "higher grade" refers to those containing at least 8 carbon atoms.

Preferred copolymers, however, are copolymers with polyfunctional acrylates as previously described herein, such as acrylates of trimethicol propane, neopentyl glycol, polybutadiene-derived polyols, and polyepoxides.

Generally, copolymers are formed from formulations with about 25 to 75 weight percent of polyfunctional acrylates, or ester mixtures of this invention balanced with other acrylates.

In FIG. 1, the lower electrode 10. dielectric coating 11,
and a capacitor with an upper electrode 12 is shown schematically.

Lower electrode 10 may be aluminum foil.

The dielectric coating 11 is a multifunctional acrylate polymer and is formed by depositing one of the acrylate structures described above on the surface of the electrode IO, for example by vacuum deposition, roller coating, or any suitable polymerization method.

Leads 13 and 14 are the upper and lower electrodes 10.12, respectively.
It is connected to the.

Another embodiment of the invention is a method of manufacturing a capacitor.

The method includes forming a dielectric coating of at least one polymer of a multifunctional acrylate as described above on a substrate and depositing an electrode layer on the dielectric coating.

This coating has a flowing (f 1 owi
ng, 'spraying, dipping, brushing
ushing), roller coating (roller
coating), spin coating (spi
n coating), drawing down (dr
by the usual method such as ``awing down''.
It can be prepared by adding the polymer to a solution in an optionally substantially inert medium and then evaporating the medium used.

It is usually desirable to use a film of multifunctional acrylate monomer and subsequently polymerize it by any of the methods described above.

It is particularly desirable to use electron beam polymerization.

This is because such methods can polymerize monomer structures very quickly without the use of additional curing factors. This also allows very thin coatings to be produced economically.

According to one embodiment of the method of the invention, the substrate itself is a conductive material that can be used as one electrode, thus forming a capacitor with two electrodes and a dielectric coating separating them. FIG. 4 shows the procedure of this embodiment. This embodiment will also be explained in the following example.

Example 22 A uniform prototype capacitor is prepared by laying down a layer of the structure of Examples 1-11 on an aluminum foil substrate, polymerizing the monomer layer by contacting it with an electron beam, and depositing metallic aluminum thereon. It was manufactured by

The thickness of the aluminum foil electrode is 12.5 microns, the thickness of the dielectric layer is 3-6 microns, and the thickness of the deposited aluminum electrode is 300-500 angstroms (o,
03 to 005 microns).

The area of the prototype capacitor was approximately 2.54 square centimeters (1 square inch). The loss factor of this capacitor was measured at 60Hz using an AO bridge.

2 and 3 illustrate the relationship between temperature and dissipation factor for the typical prototype capacitor described above.

Here, the multifunctional acrylate compositions of Examples 1 and 2 were polymerized by 15 and 10 megarad electron beams, respectively, to form dielectric coatings.

As is clear from the figure, the loss coefficient is 0.3 inches or less over the range from 30°C to 130°C.

The following table ■ uses the aforementioned multifunctional acrylate configuration,
The loss coefficients at various temperatures for other types of capacitors made using the method described above are shown.

According to another method of another embodiment of the present invention, electrode layers and dielectric coatings are arranged in alternation, as described in the aforementioned US application Ser. No. 620.647.

Capacitors formed in this way have particularly advantageous properties, such as high efficiency, being able to operate at high temperatures, being electrically stable for long periods of time, and being advantageous against malfunctions.
It also has applicability in a wide range of capacitances.

Some advantageous properties of such capacitors are explained in each section below.

Example 23 A capacitor approximately 18 baits wide was formed using the method described in the aforementioned US Application No. 620.647. The substrate was 50 micron thick aluminum foil. Dielectric layers (approximately 1 micron thick) and electrode layers (approximately 200-500 angstroms thick) were laid down alternately.

The dielectric layer was prepared by evaporating the product of Example 12 at 375°C and
It was deposited on the electrode surface maintained at 4° C. and then subjected to electron beam polymerization. Further, the electrode layer was formed by vacuum evaporation of aluminum.

The capacitors ultimately included 1000 dielectric and electrode layers each.

This loss factor is measured at 60Hz over a temperature range of 30-150'C and varies from a maximum value of 310% at 30'C to 1
It changed to a minimum value of 0.300 cm at 50°C.

24 Using the method described in Example 23, a capacitor was formed using the polymer produced in Example 17 as the dielectric.

The product was laid down by evaporating at 40°C and depositing at 48°C. The thickness of the electrode layer is 300-500
angstrom, and each capacitor is 200 angstroms.
dielectric layer and an adhered electrode layer.

The loss factor is 10 over the temperature range of 30-130°C.
Measured at 0Hz, 90-13 from the maximum value of 28 at 30℃
It changed to the minimum value of 07% at 01:.

Example 25 Capacitors formed by the method of Example 23 (optional with different number of layers and dielectric layer thickness) were cut to various sizes to obtain specific capacitance values. Further, long-term tests were conducted under the AC voltage and temperature conditions shown in Table 1 below. Until the end of the test period, none of the capacitors Φ worked normally.

1000 1.2 0.2, 20 i3o so.

Zoo 1.1 0.19 50 85 664500
1 2 20130112.3 (508577) These results show that this type of capacitor is stable at relatively high temperatures and over long periods of operation.

Takumi - An example! A uniform prototype capacitor was manufactured by the method of Example 22 from the compounds of Examples 2, 13, and 15 to 17, and the loss factor of this capacitor was measured. The results are shown in the following table.

Table V 12" 2.7 0.40 0.15 13 0.85 1.10 0.95 15 0.75 0.05 0.02516 0.95
0.70 1.95 17 1.7 0,10 0.12 As is clear from this table, the capacitor of this invention is
It has a wide range of applications and is characterized by an extremely low loss coefficient at both high and low temperatures.

Example 27 A prototype capacitor was made by the method of Example 22 using 1,2-hexadecanediol diacrylate (product of Example 21) as the dielectric.

The loss factor of this capacitor is from 08 to 110℃ at 30℃
It changed to 0.45 of or 06 of 150°C. Also, the change in capacitance is 8°C with the value at 30°C as the reference value.
The temperature changed from +1 or 2 inches at 0°C to 108 inches at 150°C.

From these results, when used as a dielectric for a capacitor, the homopolymer is characterized by a particularly small change in capacitance over a wide temperature range.

Example 28 Example 22 from the product of Example 19 and the corresponding diacrylate
A prototype capacitor was manufactured using the following method.

The loss factor of the tested capacitors formed from the product of Example 1 varied from a minimum of 0.3% at 30°C to a maximum of 1.45% at 150°C. The loss factor for capacitors formed from diacrylates varied from a maximum value of 2.7 inches at 30°C to a minimum value of 0.15 inches at 130°C.

As is clear from the foregoing, capacitors containing the polymer of the present invention as a dielectric have a wide range of applications, have extremely low loss coefficients at both high and low temperatures, and exhibit small capacitance changes over a wide temperature range. It has characteristics.

In addition to the capacitor structures described above, the invention can also be applied to wound roll or other types of capacitors. The dielectric coating may optionally be a self-supporting film instead of adhesively disposed on the electrode substrate.

[Brief explanation of the drawing]

FIG. 1 is a configuration diagram of a capacitor according to an embodiment of the present invention, FIGS. 2 and 3 are characteristic diagrams of a capacitor according to an embodiment of the invention, and FIG. 4 is an embodiment of the invention. FIG. 3 is a process diagram showing the steps of a method for manufacturing condensate. 10... Electrode, 11... Dielectric coating, 12
...electrode, 13.14...lead. Patent Applicant: General Electric Company Representative Patent Attorney: Noriyuki Numa, Patent Attorney: Nobuyuki Matsuhara, Attorney: Kiyoshi Muraki, Attorney: Fufu, Same as Hei 1) Yufu Tadashi, Attorney, Same as above Atsushi Shima - Sub-Agent: Hitoshi Suzuki Engraving of the drawing (no changes to the content) za e, continuation of the first page ■Int, CI,' Identification code Internal reference number H01G
4/18 7364-5E Priority claim [Phase] 1 m 12419 days 0 United States (U.S.
S) [Phase] Listen 7261 m 12419 days 0 United States (U
S) [Phase] 562873 [Phase] 1 m December 19th [
phase] United States (US) [phase] 5628 AI 01 Kang C rod December 1
9th [Phase] United States (US) [Phase] 5628 Father-in-law @ Inventor Timothy Lyria United States [Mu O'Donnell, U.S. 8, 12308. New York State, Schenectadale Avenue, 104 Procedural Amendment (Voluntary) January 28, 1985 Patent Application No. 266077 Relationship to Case Patent Applicant Name General Electric Company 4.1
! Agent (2) Priority Certificate 7, Contents of Amendment (1) Attach appropriate drawings as shown in the attached sheet. (2) Attach the priority certificate as shown in the attached sheet. 8. List of attached documents (1) Drawings

Claims (1)

Claims: 1. A capacitor comprising two electrodes separated by a dielectric member, said dielectric member comprising at least one polyfunctional acrylate polymer having the chemical formula: However, 几1 is a hydrocarbon or a substituted hydrocarbon radical containing at least 4 carbon atoms, 几 is a hydrocarbon or an alkyl radical containing 1 to 5 carbon atoms, and m is 2 and 6. 2. In the capacitor according to claim 1,
A capacitor in which 几2 is hydrogen or methyl, and n is 2 or 3. 3. In the capacitor according to claim 1 or 2, the polyfunctional acrylate has a group capable of reacting with an aliphatic polyhydric acid compound containing 4 to 20 carbon atoms, acrylic acid, or a derivative thereof. and the number average molecular weight is approximately 10
Capacitors obtained from polymers ranging from 00 to 5000, or from aromatic dieboxides or polyepoxides. 4. In the capacitor according to any one of claims 1 to 3, the polyfunctional acrylate is trimethylolpropane triacrylate, neopentyl triacrylate, etc.
Glycol diacrylate, paisphenol A diacrylate, diacrylate of dieboxide obtained from paisphenol A and ethoxylated derivatives thereof, diacrylate of α, w alkanediochar containing an average of 12 to 20° carbons, and number average molecular weight The capacitor is selected from the group consisting of diacrylates of butadiene resins having a molecular weight of approximately 3,000. 5. A capacitor according to any one of claims 1 to 4, wherein the polymer is formed from a mixture of polyfunctional acrylates. 6. In the capacitor according to any one of claims 1 to 4, the polymer has at least one monoacrylate having the following chemical formula
and at least one metal compound. where R is a hydrocarbon or substituted hydrocarbon radical containing about 4 to 25 carbon atoms. 7. In the capacitor according to claim 6,
The monoacrylate is cyclohexyl methacrylate. 8. In the capacitor according to claim 1,
The dielectric member has at least one compound having the chemical formula (1).
A capacitor comprising a polymer of a polyfunctional acrylate or a mixture of this acrylate and at least one ester having the formula: where Bl is an aliphatic radical, cycloaliphatic radical, or mixed alicyclic radical having about 10 to 40 carbon atoms, optionally containing about 3 or more nonconjugated olefinated bonds, and R2 is hydrogen or methyl, R6 is an aliphatic hydrocarbon radical containing about 2 to 20 carbon atoms and liberated from acetylene and polymerizable ethylenically unsaturated bodies, and n is a value between 2 and 4. m is less than n and has a value between 1 and 3, and at least 50X of the carboxyl moiety of the chemical substance is
The following chemical formula % Formula % 9. The capacitor according to any one of claims 1 to 8, wherein each electrode is an aluminum mat. 10. The capacitor according to claim 9, wherein the dielectric member is a polymer in which all structural units are obtained from the polyfunctional acrylate having the chemical formula (2). 11. In the capacitor according to claim 10, the dielectric member is a copolymer of the polyfunctional acrylate and at least one of acrylates of higher monohydroxy alcohols, higher monomers, boxides, polyols, and polyepoxides. capacitor. 12. In the capacitor according to claims 8 to 11, Bl is at least 1 in one chain.
Capacitor with 8 carbon atoms. 13. The capacitor according to claim 12, wherein the capacitor 1 is a chain radical having a branch. 14. In the capacitor according to claim 13, the polyfunctional acrylate has the following chemical formula. 1 0H200-OH=OH. A capacitor having any one of 1 1 0. However, r and S are each 7 or 8, and the total of r and S is 15. 15. The capacitor according to claim 14, wherein the polyfunctional acrylate has the chemical formula (2). 16. The capacitor of claim 8, wherein R1 is at least one of an aliphatic or cycloaliphatic radical containing about 20 to 40 carbon atoms and optionally about 3 or more olefinic bonds; A capacitor in which at least about 401% of the R1 radicals include alicyclic moieties. 17. The capacitor according to claim 8, wherein Bl is obtained from at least one polyhydroxy compound formed by reducing at least one of the corresponding polycarboxylic acid or its ester. 18. The capacitor according to claim 17, wherein the polycarboxylic acid is a dimer of linoleic acid. 9. The capacitor according to claim 18, wherein the polyhydroxy compound has a chemical formula with dotted lines as single bonds or double bonds. 2. A capacitor according to claim 1 or 8, wherein Bl has the chemical formula 20HOH2- (2), where B4 is an alkyl group having about 8 to 28 carbon atoms. 21. A capacitor according to claims 1 to 20, wherein male is hydrogen. 2. In the capacitor according to claim 21, B4 has the chemical formula R'OH2, where BS is an alkyl group.
capacitor with. 23. The capacitor according to claim 22, wherein 5 is a linear alkyl group having about 9 to 17 carbon atoms. 2. The capacitor according to claim 23, wherein B4 is n-tetradecyl. 25. In the capacitor according to claim 1 or 2, the dielectric member is made of a dielectric material in which all constituent units are a polymer obtained from an ester mixture having the chemical formula:
vinegar. 26. The capacitor of claim 25, wherein about 70-90% of the carboxyl moieties have the formula W. 2. The capacitor according to claim 26, wherein the ester mixture comprises a polyhydroxy compound having the chemical formula ER1(OH) and a polyhydroxy compound having the chemical formula CH2='O-
A capacitor formed by sequentially reacting a first carboxylic acid having the formula ROOOH and a second carboxylic acid or functional derivative thereof having the chemical formula ROOOH. However, in the polyhydroxy compound, Bl is
an aliphatic, cycloaliphatic, or mixed alicyclic radical having about 10 to 40 carbon atoms and optionally containing about 3 or more nonconjugated olefinic bonds;
is a value between 2 and 4; in the first carboxylic acid, B is hydrogen, methyl, or a functional derivative thereof; and in the second carboxylic acid or a functional derivative thereof, B
S is an aliphatic hydrocarbon radical containing about 2 to 2 o carbon atoms and free from acetylenic and polymerizable ethylenic unsaturation, and the molar ratio of the first acid to the second acid is 1:1
It is. 28. The capacitor according to claim 27, wherein R2 is hydrogen and R6 is ethyl. 29. The capacitor of claim 28, wherein R is a branched radical having at least 18 carbon atoms in one chain. 30 In the capacitor according to claim 29, R is such that r and S are each 7 or 8, and r and S
A capacitor having the following chemical formula, with the sum of 15. 31. The capacitor of claim 31, wherein the polyhydroxy compound is first reacted with the first acid and then reacted with the second acid. 32. The capacitor of claim 31, wherein the molar ratio of said first acid to said second acid is about 1.
, 7 to 1, 9:1 capacitor. 33 comprises at least one polyfunctional acrylate having the following chemical formula a cyclic radical, R is hydrogen or methyl, and n is a value between 2 and 4; and at least about 40 of the polyfunctional acrylates contain alicyclic moieties. 34 In the substance described in claim 33, R
is a chemical substance that is hydrogen. 35. In the material according to claim 33 or 34, R is at least one polyhydrochloride having the chemical formula (OH) n, formed by reducing at least one of the corresponding carboxylic acids or esters thereof. A chemical substance obtained from a compound. 36. The substance according to claim 35, wherein the polycarboxylic acid is a linoleic acid dimer. 37. In the substance described in claim 36, the polyhydroxy compound is a chemical substance having the following chemical formula, with dotted lines representing single bonds or double bonds. 38 A chemical substance comprising a mixture of esters having the chemical formula ■ and the following chemical formula (XIV) 0 1 /(00-0=OH2) ny 1 . provided that R is an aliphatic radical, alicyclic radical, or alicyclic mixed radical having about 10 to 40 carbon atoms and optionally containing about three or more nonconjugated olefinic bonds, and R2 is hydrogen or methyl, and 6 is an aliphatic hydrocarbon radical containing about 2 to 20 carbon atoms and free from acetylenic and polymerizable ethylenic unsaturations, and n is between 2 and 4. and m is less than n and is between 1 and 3, and at least about 50 of the carboxylated moieties in the chemical have the chemical formula -00-0=OH. l 2 . 39. The material of claim 38, wherein about 70 to 90 of the carboxylated moieties have the chemical formula W. 40 by sequentially reacting a polyhydroxy compound having the chemical formula R'(OH) with a first carboxylic acid having the chemical formula CH2=C-COOH and a second carboxylic acid having the chemical formula R0OOH or a functional derivative thereof. and in said polyhydroxy compound, R1 is an aliphatic radical, an alicyclic radical, or a mixed alicyclic radical having about 10 to 40 carbon atoms and optionally containing about three or more non-conjugated olefinic bonds. is a radical, and n is a value between 2 and 4, and in the first carboxylic acid, R2 is hydrogen, 1
and in the second carboxylic acid or functional derivative thereof, B3 is an aliphatic acid containing about 2 to 20 carbon atoms and free from acetylenic and polymerizable ethylenic unsaturation. a hydrocarbon radical, and the molar ratio of the first acid to the second acid is 1:1.
Ester mixture made to be. 41. The mixture according to any one of claims 33 to 40, wherein B2 is hydrogen and R6 is ethyl. 42. The mixture according to any of claims 33 to 41, wherein R1 is a branched radical having at least 18 carbon atoms in one chain, an ester mixture. 43 In the mixture according to any one of claims 33 to 42, Bl has r and S of 7 or 8, respectively.
and the sum of r and S is 15, an ester mixture having the following chemical formula. 44 In the mixture according to claim 43,
The polyhydroxy compound is an ester mixture which is first reacted with the first acid and then reacted with the second acid. 45 In the mixture according to claim 44,
The molar ratio of the first acid to the second acid is about 1.
7 to 1.9:1 ester mixture. 46. An addition polymer of the chemical substance according to any one of claims 33.38 and 40. 47 In the polymer according to claim 46,
The polymer is a homopolymer or copolymer having at least one of higher monohydroxy alcohols, higher monoepoxides, polyols, and acrylates of polyepoxides. 48. A polymer according to claim 46 or 47, wherein all constitutional units are derived from the ester mixture. 49% A patent comprising forming a dielectric coating, which is a polymer of at least one polyfunctional acrylate according to claims 1 to 32, on a substrate, and depositing an electrode layer on the dielectric coating. Claim 1
A method for manufacturing a capacitor according to items 32 to 32. 50. The method of manufacturing a capacitor according to claim 49, wherein the dielectric coating is formed by laying a multifunctional monomer film and then polymerizing the film. 51. The method of manufacturing a capacitor according to claim 50, wherein the monomer film is polymerized by an electron beam.